Mohammed et al. [32] and other workers [33–35] have reported a number of reasons for the poor performance of these materials during the hydrotreatment reactions. Depending on the nature of the support, enhanced reaction temperatures favor catalytic cracking associated with catalyst acidity.
For example, according to Duan et al. [36], an acidic 5 wt.% Pd/Al-SBA-15 catalyst produced almost 100% sunflower oil conversion with 73% yield of C15 to C18 alkanes at 250 8C. However, when the temperature was raised to 300 8C the yield dropped to 53% due to C–C bond breakage associated with combined effect of high temperature and catalyst acidity.
HDC may dominate the HDO reaction thereby increasing the ratio of odd/even number of carbon chains.
This contributes greatly to product fission and the formation of lighter unwanted species (i.e. C1 to C4 hydrocarbons). Noble metals are susceptible to sintering at elevated temperatures and could therefore experience
activity decay with time. Chu and Ruckenstein [37] showed Pd particles supported over alumina to sinter at 500 8C in H2 atmosphere. The crystallite particles of 5.5 nm size sintered to 9 nm after 6 h and later to 16.2 nm when the temperature was raised to 650 8C for 3 h.
HDO reaction proceeds with the elimination of water molecules (see Scheme 1) that can poison the active noble metal sites.
In addition to all these inconsistencies, the noble metals were proven to be expensive, making the overall
process unviable.
Therefore, accounting for a shift to alternative materials.
Catalyst deactivation may also be encountered depending on the feed stock or reaction parameters. For example, the work of Madsen and co-workers [38] showed the activity of a 2 wt.%Pd/Sibunit to depend on these factors at 300 8C. When the reaction was carried out with 5% H2 in Ar as sweeping gas, excellent yields of hydrocarbons with potentials for jet fuels were obtained but the catalyst deactivation properties depend on the feedstock nature.
The respective initial yields for stearic acid, ethyl stearate and tristearin were >90, >90 and 85%, but these values reduced to 75,62 and 25%, respectively after 75 h of reaction.
The worst scenario was observed when the reaction was performed in 100% Ar atmosphere.
In this case, the respective yields dropped to 3, 0 and 0% due to complete catalyst deactivation.
The catalyst deactivation was attributed to coke deposition and the presence of impurities like fatty acids and metals.